Vat dyestuffs of the anthraquinone series and a process of preparing them



, the nuclei of cliphenyl-ether carboxylic acid chloparticular case. J n i The condensation is 'efiected by'heating the re- Patented; Nov. 14,- 1933. o

T D STATES VAT limsrurrs seems ANDA OFVTH'E ANTHRAQUIVNY'ONE' V PROCESS-10F" PREPARING @Johann "Rosenbach, vWiesbaden and Willy Lassmann, I Frankfort-on the-Main, Germany,

. I assignors to General Aniline Works,Inc.,' New York, N."Y., a corporation of Delaware N0 Drawing. Application December 15, 1931, Serial No; 581,268; and in Germany December mom (cl-Q zoo-1601 QThe present invention relates to vat dyestufis and to a process of preparing them.

, -More particularlyit relates to a process vvhich comprises condensing an u-amino-anthraquinone compound with a compound-of the general struc ,ture;

wherein x'standsifor E f inert solvent;

no 4-inethoxy anthraquinone or the like."

As compounds of the above general jforniula theremay be used, for instance, diphenylethers and benzophenones containing orieCOCl-f-group,

for instance, in 8-' orS4-position or suchJcompounds as contain'two COCl 'groups, for inestance, in 4.4 3.3--, ,4.3'- or 4.2--'--position'.' In

. rides or, benzophenone carboxylic a'cidchlorides there may also be containedsubstituents in any positions without the condensation with r-aminoanthraquinone compounds becoming inoperative thereby. v

an equivalent thereof,for instance, carboxylic acid bromides? As solvents there may be used, for instance: nitrobenzene', chlorobenzene, 1 pure; or I technical" trichlorobenzene, benzene or an excess of the diphenylether-carboxylic' acid chloride or, benzophenone-carboxylio acid chloride e i e h' action components, preferably at a temperature between about 80 C; and. about 210 In some cases, it is also advantageous to add to the 're-j action mixture an acid binding agent,jsince dur- 5o; ing the reaction halogen hydracid is set free.

I I v wherein X standsior "3 Instead of the above mentioned carboxylic acid-- chl'oridesthere maybe used with thesan e result general structure:

7 In thismannr 16W dy f c sfil fis of thefollo tin are obtainable For'the most part theyhave a. yellowito red-:shadepthey dye the animal and dyeingpower; as compared with the known acyl-V derivatives of aminoeanthraquinones obtainable, for instance from benzoicvacid "or naphthoic acid.

In 'view'oi thesejproperties and-of the very ood fastness properties thenew dyestufis constitute a valuable. enrichment of. theclass of vat' dyestufis.

' The followingexamples serve to-illustrate the (invention; but they arenotintended to limit it thereto, the'parts being-by weight;

(1 10 parts of 4J1 '-diphenylether dicarboxylic acid; chloride, [obtainable by treating 4.4fdi-- phenylether dicarboxylic acid with phosphorus pentachloride f( cf.fU. S, Patent no. 11179124) P O FICE- I a or a group of the mmwmgjgenera ivegetable fiber'from thevat-clear tints'and possess V a'very greataflinity for thefiber and a great and 15:.2 'parts of l-amino-anthraquinone are 7 heated "in 600 parts of nitrobenzene for several hours at about 120 C; The dyestufi" separates in theforrn iof a yellow, crystalline precipitate It isvfiltered by suction, while hot-washed first with warm nitroloemzene and then. -vvith alcoholand dried; The'yi'eld is good; The dyestuif is a yel-- f low, crystal-line productwhich is soluble in'warm chlorobenzjene, nitrobenzene, and trichloroben:

zene, dissolves in strong sulfuric acid to an (2) 28 parts of flAl-diphenylether-dicarbo iylic.

acid chloride are dissolved in 1200 partsof nitrobenzene and 65.1 parts of lamino 5-benzoyl aininmanthraquinone are added thereto. After stirring for several hours at about 120 (2., the

yellow precipitate is filtered by suction, Washed. with a small quantity of alcohol and dried. The

dyestuff is diilicultly soluble in trichlorobenzene sulfuric acid to a brownish-red solution. It dyes theanimal and vegetable fiber from a Bordeaux red vat intense, bright yellow tints of excellent fastness properties.

acid chloride and 34.4 parts of L-aminO- i-methoxy ant'hraquinone are heated in 600 parts "of nitrobenzene for several hours at 150 C. The

dyestufi', which precipitates, is filtered by suction,

washed with alcohol and dried. It is obtained in a goodyield and forms an orange-red'product which dyes cotton from the alkaline hydrosulfite vat very fast orange tints.

By using instead of l-aminoi-methoxy-anthraquinone, 1-arnirio-4-benzoylamino-anthraquinone, a product is obtained which dyes the r 34.4 parts of 1-amino-5-benzoyl-amino anthra- 'quinone in 100 parts of trichlorobenzene andthe On,

whole is kept boiling for half an hour. cooling, the dyestuff precipitates from the solu tion, it is filtered by suction and washed with benzene and alcohol. .It dyes cotton from the alkaline hydrosulfite vat intense, bright yellow tints.

ample 4 in benzene withl-aminoranthraquinone,

aproduct is obtained which-dyes cotton and wool V 7 from the vat yellow tints.

(6)- 34 partsof '1-amino-5-benzoylaminoan-' thraquinone are heated-to boiling-with 1000 parts of trichlorobenzene and 34 parts' of 4-benzoyldiphenylether-'-carboxylic, acid chloride are-v added to the hot solution. .The solution is kept boiling for half an hour and the'dyestufi, which precipitates on cooling, is filteredby suction. It; dyes cottonfronr the alkaline 'hydrosulfite vat bright yellow tints;

(7) I By using in Example 6 insteadof l-amino- 5 benzoylamino anthra'quinone, l-amin'o-lmethoxyanthraquinone; a product is obtained which dyes cotton orange tints.

(8) 132 parts of j 1-amino 5-benzoyl-aminoanthraquinone are introduced into a solution of 10 parts of 4-rnethyl-benzophenone-4carboxylic acid chloride (obtainable according toAnn'alen'der Cheniie 312, page 94) in 600 parts of ,nitrobenzene and the whole is stirred forseveral hours at about 180 C. By this operation a yellow dyestuff' is precipitated which may be recrystallized from chlorobenzene. It dyes cottonffrom a violet vat I intense; yellow tints of excellent fastness properties. The dyestuff dissolves in concentrated sulfuric acid to an orange solution. It is obtained inagood yield.

' parts of nitrobenzene is then added to the acid chloride solution and the whole is stirred for sevilicacid chloride and 4%.? parts of l-amino -5- benzene and nitrobenzene.

poundof the general structure:

. 4,-methoxy-anthraquinone,

(9) 1 0 parts of benzophenone exl-dicarboxylic acid are dissolved in 34.- parts of phosphorus oxychloride and 16 parts of phosphorus pentachloride are introduced in this solution. After heating for eralhours at about 180 C. On cooling, the dye-- stuff separates in the form of a violet; crystalline and nitrobenzene; it dissolves in concentrated H ,very good fastness properties. The yield is good. (3) 20 parts of diphenyletherlA-dicarboxylic .(10)v 20 parts of benzophenone-4A'-dicarboxybenzoyl-amino-anthraquinone in 600 parts of nitrobenzene are stirred for several hours at about 180 C. The dyestuff separates in the form of a yellow;- crystalline precipitate. It is difiicultly soluble in solvents of high boiling point as, for instance, trichlorobenzene and nitrobenzene; it dissolves in concentrated sulfuric acid to an orange-red solution and dyes the animal and vegetable fiber from a Bordeaux-red vat intense, bright yellow tints'of excelle'n'tfastness properties.

(11) 10 parts of benzophenone-xl-dicarboXylic acid chloride and 16.4.parts of l-amino--methoXy-anthraquinone are dissolved in 600 parts of nitrobenzene and the whole is stirred for several hours at about 160 C. The dyestufi thus obtained is filtered by suction at about 100 C. and washed with alcohol; it dissolves in warm solvents of high boiling point such as chlorobenzene, trichloro- It dissolves in 0011-. centrated sulfuric acid to anorange-red solution and in an alkaline hydrosulfite solution to a brown-red vat from which it dyes cotton orange tints of, good fastness properties. I

Similar products are obtainable by using instead of benzophe'nonelA' dicarboxylic acid chloride, benzophen0ne-3B' 24.3? or -l.2-.dicarboxylic acid chlorida'; 1

We clairngl I I 1. The processwhich comprises condensing an oEamino-anthraquinonecompound with a com- 125 Vi cool c r V Y I wherein X2 stands. for r and Y for hydrogen or the COClgroup, by M heating the components inthe presence of an inert solvent.- I

2. The process which comprises condensing an a-amino-anthraquinone compound of the group consisting of lv-arnino-anthraquinone, 1-aminol-amino-el-benzoyl- 1w aminoranthraquinone and ,1-amino-5-benzoylamino-anthraquinone with a compound of the following formula:

solvent of the group consisting of nitr'obenzene,

chlo'robenzene and trichlorobenzene at;- a-temi perature between about 80 C. and about"210 C.

3.. The process which comprises condensing lamino-anthraquinone with 4.4 diphenyl"-ether'-, dicarboxylic acid chloride by heating the com ponents in the presence of nitrobenzene at a temperature of. 120 C(forsome hours;

4. The process which comprises condensing 1- p a amino-4-1nethoxyanthraquinone with 5 4.4 -diphenyl-ether-dicarboxylic acid chloride by heat ing the components in the presence of nitrobenzene at a temperature of 150 C.'for' some hours.

5.. The process which comprises oondensingla amino-5 benzoylamino-anthraquinone with benzophenoneixl dicarboxylic acid chloride by heating thecomponents inthe presence of nitro-:

- benzene at atemperature of 180 C. for some hours. 7 Q

6. As new products, the compounds of the general structure:

" A-NE-C 0 wherein A stands for an a-bound anthraquinone compound, X stands for V or 0 Q and Y for hydrogen or a group of the general structure: 1 I

I A having the above meaning, having a yellow to red shade, dyeing the animaland vegetable fiber from the vat clear tints and possessing a great afiinity for the fiber and a great dyeing power. 7

7. As new products, the compounds of the generalstructure: V j

meg 7'21 nitrobenzene, dissolving inconcentrated sulfuric acidto a brownish-red solution and dyeing the vat intense, bright yellow tints of excellent. fastness properties. V

9. As a new product, the compound of the following structure:

and Y vfor a radical of the group' co nsisting' of 'o 'NH-'co" ,1 j "H I: l. I

land r ITTHCO 'r'qrko'o oflm 8. As a new product, the'compound of the following structure: I 5 1:10 a r O C r o NH-G0CsHs beingldiificultly soluble in .trichlorobenzene and animal andiveget'able fiber from a Bordeaux-red I being an orange-red product and dyeing cotton being a yellow crystalline product dissolving in from the alkaline hydrosulfite vat very fast orange concentrated sulfuric acid. to an orange red solu tints. tion and dyeing the animal and vegetable fiber 10. As a new product the compound of the foll j a 5 lowing structure: I ,80

| v i r 5 csm-oo-Nn 0 I V V I o NHOOCH5 I from a Bordeaux-red vat intense, bright yellow '90 tints of excellent fastness properties.

' JOHANN ROSENBACH. "WILLY LASSMANN.

so i a i 35 r '1 a I a V a V I v 1 g 45 v f I 1 55 r 7 Q r v 60 a I a 65 r l r i t a 31.1. I I 1 l 

